Production of industrial gases containing carbon monoxide and hydrogen



Aug. 19-, 1952 E. s. CORNER ET AL 2,607,669

PRODUCTION OF INDUSTRIAL GASES CONTAINING CARBON MONOXIDE AND HYDROGEN Original Filed Aug. 12. 1947 2 SHEETS-SHEET 1 Aug. 19, 1952 E. s. CORNER ET AL 2,607,669

PRODUCTION OF INDUSTRIAL GASES CONTAINING CARBON MONOXIDE AND HYDROGEN Original Filed Aug. 12, 1947 2 SHEETSSHEET 2 I O z 8 I E CONVERSION 4 a I u T SELEGTIVITY o 60 B IOCO I LI-l (D (B 40 5 L o (D & Z 3 0 0 i0 20 4O 5O 8O I00 MnOz CONTENT WT.%

FIG. 2.

SELEGTIVITY,- MOL a;

o 1.0 20 3o 40 so so TIME ON STREAM,MINUTE$ FIG.3.

wq QflKLMCLW Patented Aug. 19, 1952 PRODUCTION OF INDUSTRIAL GASES CON- TAINING CARBON MONOXIDE AND DROGEN Eugene S; Corner, Roselle, and Charles S Lynch, Plainfield, N. J.,- assignors to Standard Oil De.- velopment Company, a corporation of Delaware Original application August '12, 1947, serial so. I 768,247. Divided and thisapplication February 4,1948,S-erialNo.6 ,227

, 1 This application is a division of our copending a plication Serial No. 768,247 filed August 12, 1947-, now U. S. Patent No; 2,553,551 dated May 22, 1951'. The present invention is directed to a method for producingindustr-ial gases containing carbon'monoxide and hydrogen from gaseous hydrocarbons and to novel compositions which function as oxygen carriers in the oxidation of gaseous hydrocarbons.

' In many industrial processes the raw material is composed of,or essentially contains, a mixture of carbon monoxide and hydrogen. Chief amongthese processes are the so-called methanol synthesis, in which carbon monoxide and hydrogen are reacted in the presence of asuitable catalyst. to produce oxygenated organic compounds, and the Fischer-Tropsch synthesis in which carbon monoxide and hydrogen in suitable proportions are reacted in the presence of a suitable catalyst.

and under selected conditions to produce a prod-. uct primarily composed of liquid hydrocarbons. In processesof this type it is highly desirable that .thefeedligas be free from contamination with inert gaseous substances.-

The obvious way to obtain a mixture of carbon monoxide and hydrogen is to subiecta mixture. of .auhydrocarbonfsuchas methane and air to controlled combustion lThisrprocedure, however,

r'esultsin agas containing a large :quantity of.

nitr en.-. 1 This trimental dilution has led to muchstudyrand-experimentation, directed towardtheridevelopedof a method for producingthe desired .matke gas free from contaminants and.

diluents.

;.Amon the procedures which have been 133110, posed for; producing from hydrocarbons a sultrable gas mixture containing carbongmo lox'kde:

and hydro en reei m la e v -ni es :iluen as is that whicha m a i .used as an ox en c r er- The e ra p ce u e Pro osed s t me the h d oc b such as-x etbane, wi h a met l ox e until he a t r s demoted inos en content, then to reoxidize the depleted metal car: i r w th a v n ns Of t e r s d e ga es, and

again. reacting the regeneratedoxide -with" 6.

hydrocarbon. By this procedljre the gas result ing from the reaction of the hydrocarbon with the metal oxide is obtained separatelfy iromi the" gaseous residues from theoxidation ,of the metal with. air.

' While r m-h f eial hav be n need .11 Claims. (01. is- 196) fo m ssus nd 2 Y Y practically impossible to oxidize a hydrocarbon withzi-nc oxide to-carbon dioxide whereby a high selectivity to carbon monoxide can'be expected in the use of this metal oxide. Zinc oxide, however, presents the great difiieulty that at the temperature at which it will give up its, oxygen thezinc will also vaporize, giving rise to 'a diificult recovery problem. Moreover, at the temperature of operation, zinc oxide does not effect a sufliciently high conversion of the hydrocarbon.

Of the many oxides-Which might be considered useful, iron oxide, based on considerations of availability, price and reactivity with hydrocarbons, would seem to be the logical choice. When it is attempted, however, to react a hydrocarbon: such as methane with a fixed bed of iron oxide;

the course of the reaction proceeds in a direction quitethe contrary .of'that desired. At the outset the. iron oxide oxidizes the hydrocarbon completely to: carbon dioxide until an appreciable quantity of ,iree ironispresent in the reaction.

mass. From that point on some carbon Inon.

oxide is produced but at the same time large quantities of carbon are produced by'reason of the highly catalytic effect of the iron on the cracking of hydrocarbons It had beenexpected that this difiiculty of controlling the course of the reaction between the hydrocarbons and iron oxide could be ameli.- orated bv opera in ac rd ng to that t qu which has come to be known as a fluidized solid techniquein which the solid in finely divided in a risingstream of the gas to be reacted while correlating the velocity of the gaswith respect to the degree of fineness of the solid. to produce. densesuspension of the solid in th a nwh ch e SOlid is i a hly t rb ent a -z;Thedi ic e ount r d with hi procedure, however, isthat when the temperature of operation maintained within the limits calculated to give. the desired rate of reaction,

for example between about 16.00 and 2000 .F.,

for use in this process they all present diiferent,

problems when. it is attempted-actually to, use,

he 'in ther e ss.- Zinc ox de-1 hwh theore ica s ou d-s he Pur e admir l -y. I

because its oxidation potential is such that it is the iinely divided mixtf re of iron oxide and iron proves to he .very difilcult to fluidize. It appears hatzthe POW reima b me c y in this. range of temperatnres, although it is considerably belowithe melting point of .eitheijthe ironl ox-ide or, the iron, with the result that the particles ag ignerate and so notren'iain the desired state .ofsuspenjsion. This failure toremai-n'fluidizedappears v.to cause the reaction 1' fol-low sub stantially-the same icourse as that observed in fixed bed operation; a I O 1 f Accordingto the present invention, an eff cient oxygen carrier iorthe oxidation of hydracarbons is prepared by mixing manganese dioxide with I selectivity.

iron oxide in such a manner as to give a very intimate degree of mixing. The intimacy of admixture desired is comparable to that attainable by precipitating the mixed oxides'from mixed water solutions of their salts. A comparable degree of mixing for the purpose of the present invention is attainable by soaking either of the oxides in a solution of the salt of the other and thereafter roasting. If desired, one of the oxides can be immersed in the water solution of a salt of the other, a precipitating agent added to precipitate the oxide of the other, and the resulting solid precipitate filtered, washed and roastedl The preferred carrier, according to the present invention, is a mixture of F6203 and MnOz conation.

taining between 10 and 70% by weight of MnOz: y

of these compounds. employed, if desired.

The oxygen carrier, according to the present invention, constitutes a marked improvement over iron oxide as an oxygen carrier both in fixed bed operation and in operation according to the so-called fluidized solid technique in which the oxygen carrier in finely divided form is suspended in the form of a dense, turbulent suspension in a rising stream of the hydrocarbon gas. In the fixed bed type of operation the compound oxygen carrier makes possible the realization of a degree of conversion and a selectivity of the reaction toward the production of carbon monoxide and hydrogen unexpectedly superior to that attainable by the use of either component of the compound carrier alone. In the fluidized solid type of operation there is secured, in addition to the foregoing advantage, considerably increased fluidizability at the temperatures of operation, which are usually between about 1600 F. and 2000 F. It will be understood that the upper limit of this temperature may be higher and is dictated only by the melting point of the finely divided solid and the material of whic thereaction vessel is made. i Furthermore, the compound carrier makes possible an operation at a high conversion level with high selectivity to carbon monoxide for an extended period of time indicating that there is no critical oxygen content of the compound car-' rier but that it is effective over a fairly wide range of oxygen content. This is important commercially because in a two-stage operation, in one stage of which the hydrocarbon is reacted with the oxygen carrier and. in the other stage of which the oxygen content of the carrier is replenished by treatment with an oxidizing agent such as air, much less careful control is required in both stages. Finally it is to be observed that the foregoing advantages are realized in both fixed bed and fluidized solid operations with a minimum production of carbon.

In one particular embodiment of the present invention, namely that in which the fluidized solid technique is employed, the fluidizing character of the solid is improved by incorporating in it varying amounts of magnesia and/or chromium oxide which may be included in the composition of the oxygen'carrier by coprecipitation with the components of the carrier. From 10 to 40% by weight of the magnesia and/orchromium oxide may be advantageously. included in the composition to improve fluidizing characteristics and in some instances to improve conversion and The nature of the present inventionwill be i .nfore'fully understood from the following dephase drawoff principle. 20-

Referring to the drawing in detail, numeral I designates a reaction vessel and numeral 2 designates a regeneration vessel. In the embodimen-t shown these vessels operate on the dense It will be understood that these vessels can be of the well known bottom drawoif type or the strictly upflow type.

Vessel l is provided at its bottom with an inlet 2 for gas and finely divided solid and at itsupper end with an outlet 3 for gas, ahead of which is an internal cyclone 4 or other separator for gases and solids having a dip leg 5 depending into the vessel. On one wall the vessel is. provided with a duct 6 having its open upper end terminating at the selected level for the dense phase of the suspension. This duct empties into a line 1 into which air or other oxidizing gas is fed through line 8. Line 1 discharges into the bottom of vessel 2 which,,like vessel l, is provided at its upper end with a gas vent 9 ahead of which is arranged a cyclone separator [0 having a dip. leg H extending into the dense phaseof the suspension in vessel 2. is alsoprovided with a duct l2 on one of its Walls having its open upper end located at the intended level of the.dense phase of thesuspension in vessel 2. Duct I 2 empties into line 2' into which is fed. a'hydrocarbon'gas through line P3.

In carrying out the process of the present invention in the apparatus described, th vessels are charged with finelydivided-solid, the individual particles of which are an intimate mixtureof manganese. oxide and iron oxide with or without -other fluidizing additions As previously indicated, this mixture is conveniently prepared by mixing aqueous solutions'of a manganese salt:

In starting up with both vessels charged with the' finely divided solid mentioned above, the systemmaybe brought to a temperature between about 1550' and 1850 F. by feeding hot combustion gases through'lines 8 and I3. If desired, some finely divided carbon may be mixed with the initi'al charge and the system brought to temperature by burning on the carbon. When the operating temperature is obtained, a hydrocarbon gas 'is fed through lin e 13 at a velocity such as to maintain the finelydivided solid in vessel "1 in suspension in the gas in the form of a dense body in which the particles are in incessant motion.

' The velocityshould be so regulated as to produce a suspension having at least about 5% by volume of 'solids, preferably between about 10 and 25%.

The velocity 'is correlated with the amount of solids charged so as to bring the level of the dense Vessel 2 phase to a point where. it. overflows into .conduit 6. :The' gases passing 'out: f the vessel tend to carry solidsv with them. These solids ar'e separated in the cyclone 4 and returned to "the. dense suspension. v

As the solid overflows into conduit 6, and thus into line I, preheated air or' other oxidizing medium is fed in'throughline 8'at'a velocitysuch as to carry the finely divided solid into 'vess'el 2 and maintain it therein'in a'suspensio-n of the character heretofore described, the level of the dense phase of the suspension being so'regulated that the dense phase overflows"into..conduitl-2 which carries sol-id back into line-2'. 1

The heat required for the reaction invessel I is supplied primarily-as sensible heat contained in the solids returned from vessel zsupplemented by preheat imparted to the hydrocarbon' gas-fro-m the'hot exhaust gas-from vessel .=It. will be appreciated thattheillustration of the apparatus and the drawing is-limitedto'the bare essentials. calculated merely: to" depict the flow plan of the process. Design and engineering details are purposely omitted to avoid unnecessary complication. Among such details are heat exchangers, aerating'jets for the various conduits, pumps, and the like. It is repeated-that the flow plan shown is only one" of-s'everal whichmay-be used, the essential requirement beingthat the fiowplan shall include at leasttwo zones inone of'which hydrocarbon is reacted with the metal oxide mixture serving as the oxygen carrier and in the other of which the resultant metal or metal-metal oxide mixture with depleted oxygen content is treated with-an oxidizing gas so' as to replenish its oxygen-content.

Referring to Fig.-'2, curve A- shows the variation in conversion of methane at 1700- in a fixed bed reactor with a' methane feed r'ate of 100 .v./v./hr.' with compound'carriers according l0 to the present invention with varying contents of manganese oxide. Curve B shows the variation in selectivity to CO under the-same conditions with the same variations in content of MnOz: The data on the runs on which these-curves are based are as follows: L i 312 with Fe2Os =MnO2 "It will be observed that' under the'conditions of operation iron oxide alone gave a conversion'of 56% vwith a selectivity to C0 of 22%. 10% of manganese oxide increased theconversi'cn to 70% and the .selectivity"to 70%. Maximum conversion was obtained witha 50 mixture of iron oxideand. manganese oxide with a selectivity to (3010i 75%. 'As the iron-oxide decreased-below 50%atheiselectivity tended to ri'sebut the conversion fell off rapidly; vManganes oxidealone" gave :a conversion of only 22%. It =wil1be ap-' parent that over a wide variation of composition both conversion and selectivity! were maintained atahighlevel. v. .1; Referring to'Fig. 3, curve Gshowsfthewariation of selectivity .to'carbcn monoxide with time on stream when using 1a5.0750.mixtureaofiEezOs Meihmbtidafion iaiwPaoFso s -1iFiXed'bed; 1700 .11;- var "11 Time onistream,'min r 15 '30 i 55 J Methaneconversion, per cerit 100 "7.0, 94 .98 Selectivity; mol percent: C0 1 7'2 76 66 Co; 99 28 2418 C1; 0' 0 *0 *16 It will be observed fir of all that thereris a relatively short induction period in which prcdpct s c an es fro 100% 6 2 to a e at ely-hi h pe centa e .of GO; This hi h selectivity to 2 0 e sisted n e particular operat o d sc ibed for a period of about 25 minutes when it began to drop off simultaneously with the format- 1; of carbon as'shown in-curve peric high selectivity to CO with no carbon for-ma indicates the high degree of utility of the oxygen carrier for commercial operations. In 2.10011- tinuous operation as heretofore described it is relatively easy to operate so as to limit the residence time of the oxygen carrier in the methane conversion zone to less than '25 minutes. A'wide variation in residence timeis permissible without any substantial effect on the compositionbf the product gas and without any 'formation of carbon. This, of course, indicates that the oxygen carrier is effective in producing the desiredQresults over a wide range of oxygen content inthe carrier. Thus, with the use of the oxygen carrier in the present invention much less careful control of residence time of the carrier in the reactor and the degree of reoxidation of the carrier f he resenerating one is'requi'r d- J j e "In order to demonstrate the effectiveness of e: composite c ieriiifa flmdi edl y e or a ion, .a' 59. 50 mixtu e ,0: F620} and. 'Mnqzrre pared y impregnation of jFezOja withxaf w ter solution of manganese, nitrate followedflby Ldrya ing and'calcining of thei'mpregnated iron 0 de was employed in finely divided form ina uidiz'e d operation in which methane was oxid g' is O t on. the fi ely di ided solid and the'fee'd rate of the methane was regul ed ata;value of 200 v./v./hqur." The .datalobt wereas follows:

was maintained atffifiempe iiture llolii" .Me'thane oxidation :with-,50 FezO3:50MnOz' I 5 [Fluid bed operation; 1700 F.; zoo v./v./hr I j .LG'oudp f: e

ha l s ea s In :thiS ,-.operation it. .will .be observed that" selectivity :was. maintained :to the :end :of' the the regenerator.

run,'which was 45 minutes in duration. Furthermore, it will be observed that no carboniorm'ation had begun at the .end of the run. 'After 35 minutes of operation the fluidization, which upsto thattime .had been excellent, began,to show signsof impairment as indicated .by the tell-taleLoccurrence' 'of..channeling. Itiwill .be understoodhowever, that in a continuous operati'oii'of the type 'illu'sti'atedin the drawing the residence time of the oxygen carrier in the reaction zone can readily be controlled so asto be less than 45 minutes. The channeling was presumably due to decrease in oxygencontent of the carrier below the desired level. The important factjreve ale d by this data is that the oxygen carrier of the present invention performs better in the "fluidized type of operation than in a fixed bed type ofoperation.

-In -order to illustrate the nature of the improvement effected by the joint use of magnesia or 'chromiu m oxide with the iron oxide-manganese oxide carrier, runs were made employing the fluidized solid technique with three-component carriers'of these types. In the following table-are given the operating conditions and the results? ethane oxidation with. metal oxides {200 v./v./hr.; 1% quartz reactor; fluid bed operation] 38FB203 45 F620: 45 F8203 Oxide Oomposition 45 M1102 45 MnOz- 45 Mnz- J 1; l7 MgO l0 MgO l0 CrzOa Time on Stream, Min 54 62 71 43 50 62 20 Methane Conversion, per

cent; 56 83 94 62 73 91 Q6 Selectivity, Mol Percent" 7 CO 90 90 89 89 90 91 83 l0 l0 8 ll 9 l7 0 0 3 0 O O 0 TAlthough mine foregoing the 'specific Deere.

tion described employs the fluidized solids 'technique, it isv tobe understood that in the practice ofthefpresent invention a fixed bed orja co s nation of fixed bed and a fluidized solid bed may be employed. In' general, the temperature in the hydrocarbon oxidation zone is maintained in'the'rang'e'between about 1600 F. and'ZOOO. F. The pressure, may be atmospheric or" s'uperatmospheric, 'dependingjfion design and economic considerations. Pressures as high "as 600 lbs./ sq. in. are contemplated. The feed rate of the hydrocarbon gas may vary widely, depending on other operating conditions. In general, permissible feed rates will be higher the higher the operating temperature and pressure. Feed rates as low as 100 volumes of gas per volume of oxygen carrier per hour are contemplated and this feed rate may be as high as 3000 .v./v./hr. The

residence time of the oxygen carrier in the hydrocarbon oxidation zone will vary and is a function, of the circulation rates required for temperature control between the reactor and This residence time is also a function of the average oxygen to metal ratio in theoxygen carrier at which high "selectivities for 00 production are obtained. This residence time may vary from about5 to v30 minutes. In generahit is preferredto have a residence time of the oxygen carrier in the hydrocarbon-oxidation zone in the range of about 10 to 15. mine utes.v Th nature and objects of the present inventionhaving been described and illustrated, what is claimed as new and useful and is desired to be secured by Letters Patent is: z

1. A method for converting a gaseousrhydrocarbon into av gas containing carbon monoxide and hydrogen which comprises contacting said hydrocarbon at a temperature of at least about 1600 with an oxygen carrier comprisinga mixture of iron oxide and manganese oxidecontaining between 10 and 70% by weightof manganese oxide and having an intimacy of admixture equal to that obtainable bygcoprecipitar tion of the hydroxides from mixed solutions fof salts of their metals followed by heating. 2. A method according to claim 1 inwhich the oxygen carrier includes magnesia. v H 3. A method according to claim 1 in which: the oxygen carrier includes chromium oxide. l

4. In a method for converting a gaseous hydroe carbon into a gascontaining carbon monoxide and hydrogen in which the gaseous hydrocarbon is passedupwardly through a contacting zone containing an oxygen carrier in the form of.-a finely divided solid at a velocity such as to main:-

' tainsaid finely divided solid in the form Off).-

. magnesia.

densefiuidized suspension while maintaining said contacting zone at atemperature .of at least about 1600 F. and product gas is recovered from said contacting zone, the step which comprises employing as an oxygen carrier a. finelysdivided solid each particle of which contains iron oxide in intimate admixture with manganese oxide the saidmanganese oxide amounting to 1040 weight'per cent of the said finely divided solid. 5.' -A ;method according to claim .4 in which each particle of oxygen carrier, also. -contains' 6.:A method according to claim 4 in whichea'ch' particle of oxygen carrier also contains chromium oxide. 7

7. In a process for converting a gaseous hydro-' carbon into a gas containing carbon monoxide and hydrogen in which there are maintained interconnected beds of finely divided solid oxygen carrier, gaseous hydrocarbon is passed upwardly through the first of said beds at a velocity sufficient to maintain said bed in a fluidized state at a temperature of at least about 1600 R, an oxidizing gas is passed upwardly through the second of said beds at a velocity sufficient to maintain said bed in a fluidized state and at a temperature at which oxygen is addedto said carrier, product gas is recovered from, the first of said beds and finely divided solid continuously fiows from each bed to the other; the-step oi employing as an oxygen .carrieria mixture "comprising iron oxide and:manganese :oxide having. an intimacy of admixture equal toithat' obtainable by ,coprecipitation of the hydroxides from mixedsolutions of; salts of "their metals followed' zby heating, the said'manganese oxide amounting to 10-70 weight, per cent of the said mixture.

8.1A method according toclaim '7 in which the oxygen carrier also includes magnesia. it

9. A method according to claim '7 in -which the oxygen carrier also includes chromium oxide. 7

10. In a process for converting gaseous hydro carbon. into a gas-containing carbon monoxide and hydrogen in which there are maintained interconnected beds of finely-divided solid oxygen carrier, gaseous hydrocarbon is passed upwardly through the first of said beds at a velocity surficient to maintain said bed in the fluidized state, maintaining said bed at a temperature of about at least 1600 F., which process is further characterized in that an oxidizing gas is passed up wardly through the second of said beds at a velocity sufficient to maintain said bed in the fluidized state, maintaining said last named bed at a temperature in which oxygen is added to said carrier in which product gas is recovered from first of said beds and finely-divided solid continuously flows from each bed to the other, the step' of employing as an oxygen carrier, a composition containing 10-40 weight per cent of magnesia with the remainder being made of substantially equal parts of iron oxide and manganese oxide.

11. In a process for converting gaseous hydrocarbon into a gas-containing carbon monoxide and hydrogen in which there are maintained interconnected beds of finely-divided solid oxygen carrier, gaseous hydrocarbon is passed upwardly through the first of said beds at a velocity sufiicient to maintain said bed in the fluidized state, maintaining said bed at a temperature of about at least 1600 E, which process is further characterized in that an oxidizing gas is passed upwardly through the second of said beds at a velocity sufiicient to maintain said bed in the fluidized state, maintaining said last named bed at a temperature in which oxygen is added to said carrier in Whichproduot gas is recovered from first 'of said beds and finely-divided solid continuously flows from each bed to the other, the step of employing as an oxygen carrier, a composition containing 10-40 weight per cent chromium oxide with the remainder being made of substantially equal parts of iron oxide and manganese oxide.

EUGENE S. CORNER.

CHARLES S. LYNCH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,109,448 Messerschmitt Sept. 1, 1914 2,042,285 Wilke et al. May 26, 1936 2,198,560 Marshall, Jr. Apr. 23, 1940 2,513,994 Davidson July 4, 1950 

1. A METHOD FOR CONVERTING A GASEOUS HYDROCARBON INTO A GAS CONTAINING CARBON MONOXIDE AND HYDROGEN WHICH COMPRISES CONTACTING SAID HYDROCARBON AT A TEMPERATURE OF AT LEAST ABOUT 1600* WITH AN OXYGEN CARRIER COMPRISING A MIXTURE OF IRON OXIDE AND MANGANESE OXIDE CONTAINING BETWEEN 10 AND 70% BY WEIGHT OF MANGANESE OXIDE AND HAVING AN INTIMACY OF ADMIXTURE EQUAL TO THAT OBTAINABLE BY COPRECIPITALTION OF THE HYDROXIDES FROM MIXED SOLUTIONS OF SALTS OF THEIR METALS FOLLOWED BY HEATING. 